EP0902339A1 - Ein aus einer Solarzelle bestehendes Zifferblatt, insbesondere für eine Uhr - Google Patents

Ein aus einer Solarzelle bestehendes Zifferblatt, insbesondere für eine Uhr Download PDF

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Publication number
EP0902339A1
EP0902339A1 EP97115577A EP97115577A EP0902339A1 EP 0902339 A1 EP0902339 A1 EP 0902339A1 EP 97115577 A EP97115577 A EP 97115577A EP 97115577 A EP97115577 A EP 97115577A EP 0902339 A1 EP0902339 A1 EP 0902339A1
Authority
EP
European Patent Office
Prior art keywords
substrate
dial
light
exposed
intended
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97115577A
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English (en)
French (fr)
Inventor
Rudolf Dinger
Jean-Paul Randin
Yves Ruedin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asulab AG
Original Assignee
Asulab AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asulab AG filed Critical Asulab AG
Priority to EP97115577A priority Critical patent/EP0902339A1/de
Publication of EP0902339A1 publication Critical patent/EP0902339A1/de
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G04—HOROLOGY
    • G04C—ELECTROMECHANICAL CLOCKS OR WATCHES
    • G04C10/00—Arrangements of electric power supplies in time pieces
    • G04C10/02—Arrangements of electric power supplies in time pieces the power supply being a radioactive or photovoltaic source
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B19/00—Indicating the time by visual means
    • G04B19/06—Dials
    • G04B19/12—Selection of materials for dials or graduations markings

Definitions

  • the present invention relates to a dial formed of a solar cell, especially of the photoelectrochemical type regenerative, the dial being intended to power a time circuit of a timepiece or a electrical circuit of a device such as a measure or the like.
  • the invention relates more particularly a dial whose face shown at the user presents an original aesthetic aspect such than an opalescent or metallic appearance.
  • a dial for a watch whose horometric circuit is powered by a conventional silicon solar cell.
  • the dial described in this document is formed of a translucent ceramic sheet, such as Al 2 O 3 , placed above the solar cell so that it is hidden from the view of the user.
  • the translucent nature of the dial allows a sufficient amount of light energy to pass through to illuminate the cell below.
  • the solar cell and the dial which the covers are made up of two separate parts which must be carried out and assembled independently.
  • This structure has many drawbacks. In effect, such a structure increases the number of parts involved in the manufacture of a device in front of be equipped, such as a watch, and therefore complicates the construction of such a device and increases its cost price.
  • the superimposition of the ceramic sheet and the cell solar leads to an increase in the thickness of the watch. This superimposed structure also leads to create an interface where reflections occur parasites from the incident light, which is harmful to overall efficiency of the solar cell.
  • the main aim of the invention is therefore to remedy the disadvantages of the aforementioned prior art in providing a dial formed by one or more cells integrated into it, the dial presenting the user an original opalescent or metallic appearance, particularly suitable for making dials decorative, for example for timepieces, everything maintaining acceptable electrical performance for the application of the cell used as source of energy and this using a cell structure simple and economical.
  • the invention has for the purpose of a dial, in particular for a timepiece, formed of at least one solar cell of the type regenerative photoelectrochemical comprising a first substrate intended to be exposed to light radiation and a second substrate, said substrates bearing, on their opposite, electrodes between which is arranged a physicochemical system capable of absorbing light and generate an electrical voltage to terminals of said electrodes, characterized in that said first substrate is formed of a translucent material.
  • the invention also for the purpose of a dial, in particular for a timepiece, formed of a substrate having a first face on which extends at least a plurality of overlapping layers defining at least one interleaved n-i-p or p-i-n element between two electrodes, and a second face intended for be exposed to light radiation, characterized in that said substrate is formed of a translucent material.
  • the invention also for the purpose of a dial, in particular for a timepiece, formed of a substrate having a first face on which extends at least a plurality of overlapping layers defining at least one interleaved n-i-p or p-i-n element between two electrodes, and a second face intended for be exposed to light radiation, characterized in that said substrate is formed of a transparent material and in that a partially transparent metallic layer and partially reflective is deposited on said second side of the substrate.
  • the subject of the invention is a dial, in particular for a timepiece, formed of minus a solar cell of the photoelectrochemical type regenerative comprising a first substrate intended for be exposed to light radiation and a second substrate, said substrates carrying, on their face in gaze, electrodes between which is arranged a physicochemical system capable of absorbing light and to generate an electrical voltage across said terminals electrodes, characterized in that said first substrate is made of a transparent material and in that a layer partially transparent and partially metallic reflective is deposited on said second face of the substrate.
  • a dial monolithic formed of a solar cell which achieves the dual function of dial and power source electric, for example for a timepiece or similar.
  • translucent material we understand everything material which lets in part of the light incident and backscatter or reflect another part while concealing from the observer the elements behind the substrate made of such a material.
  • the substrate intended to be exposed to light radiation has a light reflectivity between 50% and 90% and preferably between 60% and 85% in the field of lengths visible waves.
  • the dial depending the invention can provide a power of the order of 1 ⁇ W or more, which is still enough to power the timepiece circuit of an electronic timepiece under these lighting conditions.
  • the substrate intended to be exposed to light radiation is made based aluminum oxide, zirconium oxide or a glass opalescent.
  • the metal of the metallic layer is chosen from the set comprising gold, aluminum, silver, platinum, palladium, nickel, titanium, rhodium and copper.
  • Dial 1 is capable of transforming a light radiation into an electric current by a process called photo-conversion to feed, via a power circuit, a timepiece circuit of the watch.
  • photo-conversion process we refer to pages 303 to 312 of the book entitled "Solar Photopiles" by A. Spainud and published by Éditions French polytechnic and university presses, ISBN 2-88074326-5 .
  • Dial 1 is formed by a solar cell of the type regenerative photoelectrochemical.
  • Dial 1 includes a first substrate 2 and a second substrate 4 comprising respectively over the entire surface of their face opposite an electrode 6 respectively 8.
  • a physico-chemical system 10 capable of absorbing light and generate an electrical voltage to electrode terminals is arranged between the two substrates 2 and 4.
  • This system 10 comprises a layer 12 of a semiconductor oxide, deposited on electrode 8.
  • Layer 12 is for example formed of a layer of titanium oxide textured.
  • This system 10 further comprises a layer 14 monomolecular dye that is adsorbed on the surface of layer 12.
  • System 10 comprises an electrolyte 16, based on non-aqueous solvent containing a redox couple, for example the iodine / iodide redox couple, this electrolyte being directly in contact with the dye layer 14.
  • the electrolyte 16 is in turn in contact with a thin layer 18 of an electrocatalyst, for example a thin layer of platinum which is deposited on electrode 6.
  • the substrates 2 and 4 are joined together, by example, by a sealing frame 20 to define a space in which the system extends 10.
  • one of the two substrates 2, 4 is made of a translucent material, it being understood that the substrate intended to produce the visible face of the dial (or exposed to light radiation) will be realized in such material.
  • the substrate 2 which is intended to be exposed to light radiation and which is made of a translucent material, layer 18 being of course transparent.
  • the electrode 8 when the substrate 4 is intended to form the visible face of the dial, the electrode 8 will also be transparent.
  • the material forming the substrate 2 has a reflectivity of the incident light radiation between 50% and 90% in the field of lengths visible waves, which gives the appearance aesthetic sought for the dial.
  • the substrate 2 can be produced based on aluminum oxide, zirconium oxide or opalescent glass.
  • the first substrate 2 has a reflectivity between 60% and 85% in the field of visible wavelengths.
  • a cell having a surface corresponding to that of a conventional watch face (of the order of 5 cm 2 ), even in low-light conditions (200 to 300 lux) delivers an electrical power allowing to power a timepiece circuit of an electronic watch, namely typically a power of 1 ⁇ W to 1.5 ⁇ W in average.
  • the electrode 6 carried by the substrate 2 is indeed heard formed of a conductive layer transparent to the light at wavelengths that correspond to absorption of the dye.
  • This electrode is made of preferably in the form of a thin layer of a mixture indium oxide and tin oxide or tin oxide and antimony oxide. It goes without saying that the skilled person may choose any other transparent conductive layer equivalent.
  • the substrate 4 which is not intended a priori to to pass a light radiation, can be realized made of an opaque and advantageously reflective material.
  • the dial 1 finally includes a hole 22 located substantially in its center to allow the passage of axes on which the watch hands are fixed intended to move above the dial 1.
  • the substrate which is exposed to light radiation can also have hour markers 24 (figure 1) forming a round of hours or other inscriptions, these indexes or inscriptions can be attached or engraved on the face of the substrate exposed to light radiation.
  • layer 12 comprising the monomolecular layer of dye 14 is deposited on the substrate 4. It is understood that according to an alternative embodiment, this layer 12 could be deposited on the substrate 2 (translucent). In this realization the electrocatalytic layer 18 can be opaque or reflective.
  • the dial 26 comprises a substrate 28 formed of a plate rigid having the same characteristics as those of substrate 2 which has just been described in connection with the Figures 1 and 2.
  • the substrate 28 comprises a first face 30 on which a plurality of layers are deposited 32a, 32b, 32c successive thin p, i, n respectively sandwiched between two conductive layers 34, 36 respectively forming electrodes.
  • electrode 34 which is arranged between layer 32c and in contact with it and the substrate 28 is transparent, this electrode 34 being the element of the cell which is intended to be directly exposed to light radiation through the substrate 28.
  • electrode 34 like electrode 36 can be formed by a thin layer of an oxide mixture indium and tin oxide (ITO).
  • the three layers 32a, 32b and 32c, forming a elementary solar cell 32 therefore define a diode, i.e. a p-i-n junction diode with an intrinsic zone, inserted between a zone p and a zone n, which can be exposed to light radiation.
  • This elementary solar cell 32 consists of three layers of hydrogenated amorphous silicon (a-Si: H) having different conductivity types to form the diode p-i-n.
  • Layer 32a of the elementary cell 32 is doped for example with phosphorus to obtain a n type conductivity.
  • the thickness of this layer is preferably of the order of 10 to 20 nm.
  • the next layer 32b of the elementary cell 32 is a layer intrinsic i which is thicker than the previous one and in which electron-hole pairs are generated when the cell is exposed to light radiation.
  • the layer 32b has for example a thickness of the order of 200 to 500 nm.
  • Layer 32c of the elementary cell is for example doped with boron to obtain a p-type conductivity. The thickness of this layer is preferably of the order of 10 to 30 nm.
  • the p-type layer 32c is the most close to substrate 28, but it is understood that according to an alternative embodiment the layer closest to the substrate 28 could be an n-type layer.
  • the substrate 28 of the dial 40 is transparent and a partially reflective metal layer 42 is deposited on an outer face 44 of the substrate, opposite side 30.
  • This layer 42 has a reflectivity of the incident light radiation between 50% and 90% in the visible wavelength range, which provides the metallic luster and therefore the appearance aesthetic sought for the dial. To get this reflectivity, we essentially act on the thickness of the metal of layer 32.
  • this layer metallic 42 has a reflectivity of between 60% and 85% in the visible wavelength range.
  • a thickness of the order of 20 nm and preferably 35 nm of this layer allows sufficient light to pass through even in low-light conditions (200 to 300 lux ) so that an elementary cell having a surface of a conventional watch face (of the order of 5 cm 2 ) provides electrical power making it possible to supply a time-keeping circuit of an electronic watch, namely typically a power 1 ⁇ W on average.
  • layer 42 will present a minimum thickness between 2 and 10 nm and a maximum thickness between 15 and 40 nm.
  • the metal layer 42 can be formed of a metal chosen from the group comprising gold, copper, aluminum, silver, platinum, palladium, nickel, titanium and rhodium. Of course others metals with reflectivity characteristics of the same order may also be suitable.
  • an intermediate layer could be provided of attachment between the face 44 and the layer 42.
  • the deposition of the metal from layer 42 can be carried out conventionally by sputtering, evaporation thermal vacuum or using a barrel electrons. This deposit can be made through a mask defining the contours of layer 42 or delimited according to photolithography techniques classics.
  • the translucent substrate of the dial according to the first aspect of the invention is replaced by a substrate made of transparent material on the outside from which a layer having characteristics has been deposited identical to those of layer 44 described in connection with figure 4.
  • dials shown in Figures 2 and 3 may include on the outer face of their respective translucent substrate a metallic layer such as that described in connection with Figure 4.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Electromechanical Clocks (AREA)
  • Photovoltaic Devices (AREA)
EP97115577A 1997-09-09 1997-09-09 Ein aus einer Solarzelle bestehendes Zifferblatt, insbesondere für eine Uhr Withdrawn EP0902339A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97115577A EP0902339A1 (de) 1997-09-09 1997-09-09 Ein aus einer Solarzelle bestehendes Zifferblatt, insbesondere für eine Uhr

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP97115577A EP0902339A1 (de) 1997-09-09 1997-09-09 Ein aus einer Solarzelle bestehendes Zifferblatt, insbesondere für eine Uhr

Publications (1)

Publication Number Publication Date
EP0902339A1 true EP0902339A1 (de) 1999-03-17

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EP97115577A Withdrawn EP0902339A1 (de) 1997-09-09 1997-09-09 Ein aus einer Solarzelle bestehendes Zifferblatt, insbesondere für eine Uhr

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2423189A (en) * 2005-02-15 2006-08-16 Martin Lister Coloured solar cell
JP2016070681A (ja) * 2014-09-26 2016-05-09 シチズンホールディングス株式会社 太陽電池付き時計
JP2016090519A (ja) * 2014-11-10 2016-05-23 シチズンホールディングス株式会社 太陽電池付き時計、及び変形痕を隠す方法
JP2016090518A (ja) * 2014-11-10 2016-05-23 シチズンホールディングス株式会社 太陽電池付き時計、及び変形痕を隠す方法
JP2017072606A (ja) * 2016-12-08 2017-04-13 セイコーエプソン株式会社 時計用文字板、及び太陽電池付電子時計

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427797A (en) * 1966-12-12 1969-02-18 Kenjiro Kimura Timepiece using a solar battery as the power source
GB1380839A (en) * 1971-12-28 1975-01-15 Suwa Seikosha Kk Solar cells and electronic timepieces incorporating the same
US3989541A (en) * 1974-09-30 1976-11-02 The United States Of America As Represented By The United States National Aeronautics And Space Administration Solar cell assembly
JPH04199751A (ja) * 1990-11-29 1992-07-20 Matsushita Electric Ind Co Ltd 太陽電池
JPH05251723A (ja) * 1992-03-03 1993-09-28 Kanegafuchi Chem Ind Co Ltd 集積型太陽電池モジュール
JPH06232435A (ja) * 1991-10-30 1994-08-19 Ricoh Co Ltd 有機光起電力素子
JPH08204216A (ja) * 1995-01-26 1996-08-09 Sanyo Electric Co Ltd 太陽電池及びその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427797A (en) * 1966-12-12 1969-02-18 Kenjiro Kimura Timepiece using a solar battery as the power source
GB1380839A (en) * 1971-12-28 1975-01-15 Suwa Seikosha Kk Solar cells and electronic timepieces incorporating the same
US3989541A (en) * 1974-09-30 1976-11-02 The United States Of America As Represented By The United States National Aeronautics And Space Administration Solar cell assembly
JPH04199751A (ja) * 1990-11-29 1992-07-20 Matsushita Electric Ind Co Ltd 太陽電池
JPH06232435A (ja) * 1991-10-30 1994-08-19 Ricoh Co Ltd 有機光起電力素子
JPH05251723A (ja) * 1992-03-03 1993-09-28 Kanegafuchi Chem Ind Co Ltd 集積型太陽電池モジュール
JPH08204216A (ja) * 1995-01-26 1996-08-09 Sanyo Electric Co Ltd 太陽電池及びその製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 16, no. 530 (E - 1287) 30 October 1992 (1992-10-30) *
PATENT ABSTRACTS OF JAPAN vol. 18, no. 603 (E - 1632) 16 November 1994 (1994-11-16) *
PATENT ABSTRACTS OF JAPAN vol. 18, no. 8 (E - 1486) 7 January 1994 (1994-01-07) *
PATENT ABSTRACTS OF JAPAN vol. 96, no. 12 26 December 1996 (1996-12-26) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2423189A (en) * 2005-02-15 2006-08-16 Martin Lister Coloured solar cell
JP2016070681A (ja) * 2014-09-26 2016-05-09 シチズンホールディングス株式会社 太陽電池付き時計
JP2016090519A (ja) * 2014-11-10 2016-05-23 シチズンホールディングス株式会社 太陽電池付き時計、及び変形痕を隠す方法
JP2016090518A (ja) * 2014-11-10 2016-05-23 シチズンホールディングス株式会社 太陽電池付き時計、及び変形痕を隠す方法
JP2017072606A (ja) * 2016-12-08 2017-04-13 セイコーエプソン株式会社 時計用文字板、及び太陽電池付電子時計

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